CN109065858A - Modified tertiary cathode material in a kind of surface and preparation method thereof and its manufactured battery - Google Patents
Modified tertiary cathode material in a kind of surface and preparation method thereof and its manufactured battery Download PDFInfo
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- CN109065858A CN109065858A CN201810827440.2A CN201810827440A CN109065858A CN 109065858 A CN109065858 A CN 109065858A CN 201810827440 A CN201810827440 A CN 201810827440A CN 109065858 A CN109065858 A CN 109065858A
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- 239000010406 cathode material Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 claims abstract description 29
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 28
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 24
- 239000001301 oxygen Substances 0.000 claims abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002407 reforming Methods 0.000 claims abstract description 10
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 6
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 6
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 6
- 229910019549 CoyMzO2 Inorganic materials 0.000 claims abstract description 3
- 229910052593 corundum Inorganic materials 0.000 claims abstract 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 39
- 238000010438 heat treatment Methods 0.000 claims description 32
- 238000005253 cladding Methods 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 14
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 239000007790 solid phase Substances 0.000 claims description 11
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 10
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 10
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 7
- 239000013067 intermediate product Substances 0.000 claims description 6
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 229910052727 yttrium Inorganic materials 0.000 claims 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 43
- 238000009792 diffusion process Methods 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 12
- 230000004087 circulation Effects 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 11
- 239000010410 layer Substances 0.000 description 11
- 241000894007 species Species 0.000 description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 10
- 235000013339 cereals Nutrition 0.000 description 10
- 229910013716 LiNi Inorganic materials 0.000 description 8
- 238000007086 side reaction Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 6
- 239000013590 bulk material Substances 0.000 description 5
- 238000000840 electrochemical analysis Methods 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- 239000010405 anode material Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 244000283207 Indigofera tinctoria Species 0.000 description 1
- 229910015746 LiNi0.88Co0.09Al0.03O2 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Manufacturing & Machinery (AREA)
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Abstract
The present invention provides a kind of modified tertiary cathode material in surface, is the clad surface modified layer on tertiary cathode material kernel；The tertiary cathode material kernel is Li1+kNixCoyMzO2, wherein M is one of Al, Mn, Ti, Mg, -0.1≤k≤0.1,0 < x <, 1,0 < y <, 1,0 < z < 1；The surface reforming layer is formed by two kinds of surface modifying species, and one kind is yttria-stabilized zirconia, another is oxide, is selected from Al2O3、SiO2、MgO、ZrO2.The present invention also provides the preparation method of the modified tertiary cathode material in the surface and its manufactured batteries.YSZ provided by the invention is a kind of oxide containing Lacking oxygen, be conducive to lithium ion mobility, pass through the modified nickelic tertiary cathode material in its surface, surface has faster lithium ion mobility rate, the surface for being covered on nickelic tertiary cathode material can improve lithium ion diffusion problem well, improve the high rate performance of material.
Description
Technical field
The invention belongs to battery material fields, and in particular to a kind of tertiary cathode material of lithium ion battery, its preparation side
Battery made of method and the positive electrode.
Background technique
Lithium ion battery is widely used on portable electronic product as a kind of novel green high-energy battery, and
It is expanded to fields such as new energy electric motor vehicles, this is to lithium ion battery energy density, cycle life, cost and safety etc.
More stringent requirements are proposed.Positive electrode is the important component of lithium ion battery, accounts for the 30%- of entire battery totle drilling cost
40% or so.Therefore, the performance for improving positive electrode is extremely crucial for the development of lithium ion battery.
Nickelic ternary layered positive electrode Li [NixCoyM1-x-y]O2(x >=0.8, M Al, Mn etc.) is considered as that can expire
One of most promising positive electrode applied enough, however, the system material as high energy lithium ion cell candidate material also
There are some problems: firstly, due to Ni during high―temperature nuclei3+It is unstable, be easy to be reduced into Ni2+And due to Li+ And Ni2+ Close ionic radius and resulting Li+/Ni2+Mixing leads to the solid phase of lithium ion
It spreads more difficult, increases the polarization of material；Secondly as the Ni easily restored4+Chemical instability, especially height
In the state of de- lithium, positive electrode surface is easy and side reaction occurs for electrolyte, generates electrochemicaUy inert layer, and along with sharp brilliant
The generation of stone phase and the equal impurity phase of rock salt, it is suppressed that the diffusion of lithium ion, at the same time along with the stream of oxygen in bulk material
It loses, reduces security performance；In addition, during removal lithium embedded, the second particle internal tiny crack as caused by multiphase transformation
It generates, causes electrolyte to be further exacerbated by the corrosion of material, surface impedance further increases.These problems synthesis results in electricity
The safety problem hidden danger for sharply declining and becoming more and more important of chemical property.
The method for promoting nickelic tertiary cathode material chemical property at present mainly has surface cladding and element doping.Patent
107331852 A of CN proposes a kind of using oxide (Nb2O5, ZrO2And Y2O3) surface coated to tertiary cathode material progress
Method, coating reduce the side reaction of electrolyte and positive electrode to a certain extent, improve the cycle performance and heat of material
Stability, but effect is limited, while can bring counter productive, because the metal oxide of cladding is inert material, it is suppressed that
The transmission of lithium ion and electronics.104995769 A of patent CN coats stratified material, cycle performance by doping oxide dry method
It is improved, but its clad has a single function the contribution of material property, merely illustrates Lacking oxygen and promotes lithium ion transport
Effect, the synergistic effect of YSZ and other materials is not mentioned, and its method is coated on finished product, using height
Warm Post isothermal treatment, is hardly formed the stratified material of surface doping, only forms certain thickness clad, exists to lithium ion
The inhibition of diffusion.105938901 A of patent CN coats stratified material by oxide dry method, and cycle performance, which has, to be improved,
But its covering amount is smaller, and without carrying out suitable Post isothermal treatment, causes clad to be difficult to be uniformly wrapped on material, wrap
Solid solid interface between coating and bulk material does not connect, and hinders the diffusion of lithium ion, and hinders the expansion of electrolyte
It dissipates.Patent CN108258224A proposes a kind of preparation method of the tertiary cathode material of surface clad oxide, not only makes
Preparation Method is cumbersome, and inert oxide surface clad can inevitably lead to first discharge specific capacity and high rate performance
Decline.
Summary of the invention
In view of problem above existing for this field, the present invention provides a kind of modified tertiary cathode materials in surface, in not shadow
Under the premise of the performance for ringing material discharge capacity itself, the cyclical stability and big high rate performance of tertiary cathode material are improved.
The present invention also provides a kind of preparation method of the modified tertiary cathode material in nano-oxide surface, the preparation method packets
Cladding process containing dry method and high-temperature post-treatment technique, the surface that the former is suitable for industrialized production is modified, and the latter helps to improve
The lithium ion conductivity of solid solid interface, it is expected that this cladding process can be in batches at the nickelic of production modification in industrial large-scale production
The performance of tertiary cathode material.
A further object of the present invention is to propose lithium ion battery made of the modified tertiary cathode material in the surface.
Realize above-mentioned purpose technical solution of the present invention are as follows:
A kind of modified tertiary cathode material in surface, is the clad surface modified layer on tertiary cathode material kernel；
The tertiary cathode material kernel is Li1+kNixCoyMzO2, wherein M is one of Al, Mn, Ti, Mg, -0.1
1,0 < y < of≤k≤0.1,0 < x <, 1,0 < z < 1；
The surface reforming layer is formed by two kinds of surface modifying species, and one of which is yttria-stabilized zirconia
(YSZ), another is oxide, is selected from Al2O3、SiO2、MgO、ZrO2At least one of.
In the present invention in YSZ material Lacking oxygen be by into zirconium oxide doped yttrium oxide form, so as to by Y3+Carry out generation
For Zr4+A part in ion.As a result, by three O2-Ion replaces four O2-Ion can finally form Lacking oxygen
(oxygen vacancy).The space as caused by the Lacking oxygen generated in this way forms very on the surface of positive active material
The space of lithium ion deintercalation can mostly be made.The path of Lacking oxygen is connected if it exists as a result, then lithium ion conduction degree can will very
Height is based on this Lacking oxygen, if by secondary cell is suitable for comprising the positive active material of the YSZ as surface-modified particles,
Capacitance loss can then be minimized.Another surface-modified particles is metal oxide Al2O3、SiO2、MgO、ZrO2In extremely
Few one kind, is able to suppress the side reaction of material and electrolyte, is coated on material surface, can resist trace in electrolyte
The integrality of nickelic ternary material is protected in the corrosion of HF.Secondly, being formed complete by dry method cladding and Post isothermal treatment process
Surface coating layer, it is suppressed that the formation of the micro-crack of material.In addition, being wrapped jointly by YSZ and another surface-modified particles
It covers, achieves unexpected synergistic effect, greatly improve the chemical property of material.
The following are the preferred technical solution of the present invention.
Wherein, yttria-stabilized zirconia content is t relative to the mass percent of tertiary cathode material kernel, wherein
0.1% < t < 5%；
Another surface modifying species content is s relative to the mass percent of nickelic tertiary cathode material kernel,
In 0.1% < s < 5%.
Wherein, in the surface reforming layer, yttria-stabilized zirconia chemical formula is Zr(1-a)YaO2-a/2, wherein 0.01 < a
≤ 0.3, range of the Lacking oxygen amount in 0.01-5000ppm.
Wherein, the granular size of the surface modifying species is 0.1-100nm.
The preparation method of the modified tertiary cathode material in surface of the present invention, is at least one of following methods:
First method is tertiary cathode material and surface modifying species to be carried out solid phase mixing cladding, after cladding
Intermediate product carries out high-temperature heat treatment process 1, obtains the modified nickelic tertiary cathode material in surface.
Second method is the presoma of tertiary cathode material, surface modifying species to be carried out solid phase mixing cladding, then
It is mixed with monohydrate lithium hydroxide, then carries out high-temperature heat treatment process 2, obtain the modified tertiary cathode material in surface；
The third method is that one of the presoma of tertiary cathode material, surface modifying species are carried out solid phase mixing
Cladding carries out high-temperature heat treatment process 2, intermediate product is obtained, among gained after then being mixed with monohydrate lithium hydroxide
Another progress solid phase mixing cladding in product and surface modifying species, then high-temperature heat treatment process 1 is carried out, it obtains to surface and changes
The tertiary cathode material of property.
Wherein, it carries out the solid phase mixing and coats the equipment used as mechanical fusion machine, roller mill, ball mill, high-energy
At least one of ball mill, planetary mill.
Wherein, the high-temperature heat treatment process 1 are as follows: 300-700 DEG C of heat treatment temperature, the time 1-10h of heat treatment.
Wherein, the high-temperature heat treatment process 2 is two sections of high-temperature heat treatments, and wherein first segment is in 400-800 DEG C of temperature
Lower heat treatment 3-10h, second segment are to be heat-treated 10-30h at a temperature of 650-900 DEG C.
Wherein, the presoma of the tertiary cathode material is NixCoyMz(OH)2.Wherein M is one in Al, Mn, Ti, Mg
Kind, 0 < x <, 1,0 < y <, 1,0 < z < 1.
Wherein, the high-temperature heat treatment process 1, high-temperature heat treatment process 2 are carried out under oxygen atmosphere.
The lithium ion battery made of the modified tertiary cathode material in the surface.
Compared with prior art, the invention has the following advantages that
(1) YSZ provided in the present invention is a kind of oxide containing Lacking oxygen, is conducive to lithium ion mobility, passes through it
The modified nickelic tertiary cathode material in surface, surface have faster lithium ion mobility rate, are covered on nickelic tertiary cathode material
The surface of material can improve lithium ion diffusion problem well, improve the high rate performance of material.On the other hand, suitable by selecting
When covering amount by nano material effectively, be uniformly coated on material surface, it is suppressed that the side reaction between material and electrolyte,
Improve the cycle performance of material.The modified tertiary cathode material embodiment 1 in the surface of the application, will for the first time compared with comparative example 1
Specific discharge capacity is by 210.6mAh g-1It is increased to 211.7mAh g-1, specific discharge capacity is by 168.3mAh g when 3C-1It is increased to
178.2mAh g-1。
(2) a kind of modified nickelic tertiary cathode material in surface, surface modifying species (metal oxide are provided in invention
Al2O3、SiO2、MgO、ZrO2) it is coated on bulk material surface, reduce the side reaction of nickelic tertiary cathode material and electrolyte,
The irreversible capacity loss for inhibiting material, improves cycle performance.The modified nickelic tertiary cathode material in the surface of the application is real
100 weeks circulation volume conservation rates for applying example 1 are 86.4%, and 100 weeks circulation volume conservation rates of comparative example 1 are only 76.4%.
(3) the YSZ material and other surfaces modified material (metal oxide provided in the present invention with Lacking oxygen
Al2O3、SiO2、MgO、ZrO2) common cladding generates a kind of unexpected synergistic effect, greatly improve the electrification of material
Learn performance.In addition, two kinds of surface modifying species covering amounts are between 0.1-5%, it is ensured that the uniformity of cladding is conducive to press down
The side reaction of prepared material and electrolyte, 100 weeks circulation volume conservation rates in embodiment 2 are 85.7%, and the 100 of comparative example 2
All circulation volume conservation rates are only 78%, illustrate that lesser covering amount can not achieve the purpose that improve material circulation performance, and
Suitable covering amount just can be with stereoscan photograph is shown, cladding substance is equably coated on material surface, it is suppressed that electrolyte
With the side reaction of bulk material.
(4) a kind of surface modification technology suitable for industrialized production is provided in the present invention, which includes dry method packet
Coating process and high-temperature post-treatment technique, the surface that the former is suitable for industrialized production is modified, and the latter helps to improve solid solid interface
Lithium ion conductivity, it is expected that this cladding process in industrial large-scale production can batch at producing modified nickelic tertiary cathode
The performance of material.
Detailed description of the invention
Fig. 1 is the first charge-discharge curve of nickelic tertiary cathode material prepared by embodiment 2 and comparative example 1.
Fig. 2 is the high rate performance figure of nickelic tertiary cathode material prepared by embodiment 2 and comparative example 1.
Fig. 3 is the cycle performance figure of embodiment 2 and the comparative example 1 nickelic tertiary cathode material prepared and comparative example.
Fig. 4 is the stereoscan photograph of the covering material of embodiment 2.
Specific embodiment
Illustrate the present invention below by most preferred embodiment.Those skilled in the art institute it should be understood that, embodiment is only used to
It illustrates rather than for limiting the scope of the invention.
In used material, nano-oxide YSZ (Zr0.92Y0.08O1.96) be it is commercially available, by grinding to obtain average grain diameter
The YSZ of 50nm, range of the Lacking oxygen amount in 0.01-5000ppm.
It in embodiment, carries out solid phase mixing and coats the equipment used as mechanical fusion machine, the time for mixing cladding is 5 points
Clock, revolving speed 2000rpm.
Unless otherwise instructed, material is commercially available in embodiment.Unless otherwise instructed, means used are this field routine
Means.
Embodiment 1
Nickelic tertiary cathode material (the molecular formula: LiNi for being 13 μm in average grain diameter0.88Co0.09Al0.03O2) core surface shape
Nano-oxide YSZ (the Zr that average grain diameter at 0.5% (mass fraction) is 50nm0.92Y0.08O1.96) and 0.5% (quality point
Number) 50nm nano aluminium oxide (Al2O3) surface reforming layer.
Preparation method is as follows:
Weigh the nickelic tertiary cathode material (LiNi of 300.0g0.88Co0.09Al0.03O2), 1.500g nano-oxide YSZ
(Zr0.92Y0.08O1.96), 1.500g nano aluminium oxide (Al2O3), it is evenly coated using mechanofusion method, then in oxygen atmosphere
The modified nickelic tertiary cathode material in surface can be obtained after 500 DEG C of heat treatment 4h.
Electrochemical property test is as follows:
Target product is mixed with conductive agent acetylene black, binder PVDF (Kynoar) according to mass ratio for 8:1:1
Uniformly, it then is mixed into the slurry of certain viscosity with NMP (N- methyl-pyrrolidon), slurry is coated uniformly on Al foil,
80 DEG C, dry 4h is washed into the electrode slice that diameter is 14mm, 80 DEG C of vacuum dry 12h is carried out after rolling.The electrode slice is transferred to
In glove box, as positive plate, then using metal lithium sheet as cathode, 2400 film of Celgard is diaphragm, 1mol L-1LiPF6/EC
+ DEC+DMC (volume ratio 1:1:1) is electrolyte, in glove box (German M.Braun company, O2And H2O mass fraction is respectively less than
2032 button cells are assembled in 0.1ppm), the battery assembled carries out charge-discharge test (China on CT2001 indigo plant electric tester
Wuhan Jin Nuo Co., Ltd), 25 DEG C ± 3 DEG C of temperature.
Electro-chemical test shows that initial charge, specific discharge capacity are respectively in 0.1C, 2.5-4.3V voltage range
236.4 with 211.7mAh g-1, first charge-discharge coulombic efficiency is 89.7%, (3C), 2.5-4.3V voltage under the conditions of high magnification
Specific discharge capacity in range is 178.2mAh g-1, 100 circulation volume conservation rates are under the conditions of 1.0C, 2.5-4.3V
86.4%.
Embodiment 2
Nickelic tertiary cathode material (the molecular formula: LiNi for being 13 μm in average grain diameter0.88Co0.09Al0.03O2) core surface shape
Nano-oxide YSZ (the Zr that average grain diameter at 1% (mass fraction) is 50nm0.82Y0.18O1.91) and 0.5% (mass fraction)
50nm nano zircite (ZrO2) surface reforming layer.
Preparation method is as follows:
Weigh the nickelic tertiary cathode material (LiNi of 300.0g0.88Co0.09Al0.03O2), 3.000g nano-oxide YSZ
(Zr0.92Y0.08O1.96), 1.500g nano zircite (ZrO2), it is evenly coated using mechanofusion method, then in oxygen atmosphere
The modified nickelic tertiary cathode material in surface can be obtained after 600 DEG C of heat treatment 4h.As shown in figure 4, cladding substance equably wraps
It is overlying on material surface, it is suppressed that the side reaction of electrolyte and bulk material.
Electrochemical property test is the same as embodiment 1；
Electro-chemical test shows that initial charge, specific discharge capacity are respectively in 0.1C, 2.5-4.3V voltage range
237.9 with 210.3mAh g-1, first charge-discharge coulombic efficiency is 88.4%, as shown in Figure 1；Under the conditions of high magnification (3C),
Specific discharge capacity in 2.5-4.3V voltage range is 176.0mAh g-1, as shown in Figure 2；Under the conditions of 1.0C, 2.5-4.3V
100 circulation volume conservation rates are 85.7%, as shown in Figure 3.
Embodiment 3
Nickelic tertiary cathode material (the molecular formula: LiNi for being 13 μm in average grain diameter0.88Co0.09Al0.03O2) core surface shape
Nano-oxide YSZ (the Zr that average grain diameter at 2% (mass fraction) is 50nm0.82Y0.18O1.91) and 2% (mass fraction)
Nano silica (the SiO of 50nm2) surface reforming layer.
Preparation method is as follows:
Weigh the nickelic tertiary cathode material (LiNi of 300.0g0.88Co0.09Al0.03O2), 6.000g nano-oxide YSZ
(Zr0.92Y0.08O1.96), 6.000g nano silica (SiO2), it is evenly coated using mechanofusion method, then in oxygen atmosphere
In the modified nickelic tertiary cathode material in surface can be obtained after 700 DEG C of heat treatment 4h.
Electrochemical property test is the same as embodiment 1；
Electro-chemical test shows that initial charge, specific discharge capacity are respectively in 0.1C, 2.5-4.3V voltage range
234.7 with 208.9mAh g-1, first charge-discharge coulombic efficiency is 89%, as shown in Figure 1；(3C), 2.5- under the conditions of high magnification
Specific discharge capacity in 4.3V voltage range is 171.1mAh g-1, as shown in Figure 2；100 times under the conditions of 1.0C, 2.5-4.3V
Circulation volume conservation rate is 86.3%.
Embodiment 4
In nickelic ternary anode material precursor (molecular formula: Ni0.88Co0.09Al0.03(OH)2) core surface formation 0.5%
Nano zircite (the ZrO of (mass fraction)2) and 1% (mass fraction) 50nm nano-oxide YSZ
(Zr0.92Y0.08O1.96) surface reforming layer after, with lithium hydroxide it is baking mixed after obtained Preburning material, using high-temperature heat treatment
2, obtain final products.
Preparation method is as follows:
Weigh 300.0g nickelic ternary anode material precursor (molecular formula: Ni0.88Co0.09Al0.03(OH)2), 1.500g receives
Rice zirconium oxide (ZrO2), the nano-oxide YSZ (Zr of 3.000g0.92Y0.08O1.96) 141.140g monohydrate lithium hydroxide
(LiOH·H2O), it is evenly coated using mechanofusion method mixing, obtains Preburning material.Then 480 DEG C of heat treatment in oxygen atmosphere
The modified nickelic tertiary cathode material in surface can be obtained after being then warming up to 740 DEG C of 20 hours of heat treatment in 4h.
Electrochemical property test is the same as embodiment 1；
Electro-chemical test shows that initial charge, specific discharge capacity are respectively in 0.1C, 2.5-4.3V voltage range
235.9 with 209.2mAh g-1, first charge-discharge coulombic efficiency is 88.7%, (3C), 2.5-4.3V voltage under the conditions of high magnification
Specific discharge capacity in range is 175.2mAh g-1, 100 circulation volume conservation rates are under the conditions of 1.0C, 2.5-4.3V
88.6%.
Embodiment 5
In nickelic ternary anode material precursor (molecular formula: Ni0.88Co0.09Al0.03(OH)2) core surface formation 0.5%
After clad of the average grain diameter of (mass fraction) for the nano magnesia (MgO) of 50nm, with the baking mixed rear system of lithium hydroxide
Intermediate products are obtained, then coat the nano-oxide YSZ (Zr of the 50nm of one layer 1% (mass fraction) again0.92Y0.08O1.96) table
Face modified layer.
Preparation method is as follows:
Weigh 300.0g nickelic ternary anode material precursor (molecular formula: Ni0.88Co0.09Al0.03(OH)2), 1.500g receives
Monohydrate lithium hydroxide (the LiOHH of rice magnesia (MgO), 141.140g2O), it is evenly coated, is obtained using mechanofusion method mixing
To Preburning material.Then it after 480 DEG C of heat treatment 4h are then warming up to 740 DEG C of 20 hours of heat treatment in oxygen atmosphere, obtains
Between product.Finally, weighing the intermediate product of 30.000g and the nano-oxide YSZ (Zr of 0.300g again0.92Y0.08O1.96), it adopts
It is evenly coated with mechanofusion method, then can be obtained surface is modified nickelic three after 600 DEG C of heat treatment 4h in oxygen atmosphere
First positive electrode.
Electrochemical property test is the same as embodiment 1；
Electro-chemical test shows that initial charge, specific discharge capacity are respectively in 0.1C, 2.5-4.3V voltage range
237.2 with 209.8mAh g-1, first charge-discharge coulombic efficiency is 88.4%, (3C), 2.5-4.3V voltage under the conditions of high magnification
Specific discharge capacity in range is 173.2mAh g-1, 100 circulation volume conservation rates are under the conditions of 1.0C, 2.5-4.3V
83.8%.
Comparative example 1
As a comparison, the nickelic tertiary cathode material (LiNi modified without surface0.88Co0.09Al0.03O2), it fills for the first time
Specific discharge capacity is respectively as follows: 235.8 and 210.6mAh g-1, first charge-discharge efficiency 89.3%；In 1.0C, 2.5-4.3V item
Capacity retention ratio is 76.4% after lower 100 circulations of part.
Comparative example 2
As a comparison, average grain diameter be 13 μm nickelic tertiary cathode material (molecular formula:
LiNi0.88Co0.09Al0.03O2) core surface formed 0.1% (mass fraction) average grain diameter be 50nm nano-oxide YSZ
(Zr0.92Y0.08O1.96) and 0.1% (mass fraction) 50nm nano zircite (ZrO2) surface reforming layer.
Preparation method is as follows:
Weigh the nickelic tertiary cathode material (LiNi of 300.0g0.88Co0.09Al0.03O2), 0.300g nano-oxide YSZ
(Zr0.92Y0.08O1.96), 0.300g nano zircite (ZrO2), it is evenly coated using mechanofusion method, then in oxygen atmosphere
The modified nickelic tertiary cathode material in surface can be obtained after 600 DEG C of heat treatment 4h.
Nickelic tertiary cathode prepared by the surface of embodiment 1-2 preparation modified nickelic tertiary cathode material and comparative example 1
Material, surface modifying species and surface modifying species amount and material assembling lithium ion battery first charge-discharge efficiency with
And it is as shown in the table in the cycle performance data of 2.5-4.3V.
1 embodiment and comparative example electrochemical property test tables of data of table
Circulating battery experiments have shown that, the modified tertiary cathode material in 1 surface of embodiment will discharge for the first time compared with comparative example 1
Specific capacity is by 210.6mAh g-1It is increased to 211.7mAh g-1, specific discharge capacity is by 168.3mAh g when 3C-1It is increased to
178.2mAh g-1。
Above embodiment be only preferred embodiments of the present invention will be described, not to the scope of the present invention into
Row limits, and without departing from the spirit of the design of the present invention, this field ordinary engineering and technical personnel is to technical side of the invention
The all variations and modifications that case is made, should fall within the scope of protection determined by the claims of the present invention.
Claims (10)
1. a kind of modified tertiary cathode material in surface, which is characterized in that be that clad surface is modified on tertiary cathode material kernel
Layer；
The tertiary cathode material kernel is Li1+kNixCoyMzO2, wherein M is one of Al, Mn, Ti, Mg, -0.1≤k≤
0.1,0 < x <, 1,0 < y <, 1,0 < z < 1；
The surface reforming layer is formed by two kinds of surface modifying species, and one of which is yttria-stabilized zirconia (YSZ), separately
Outer one kind is oxide, is selected from Al2O3、SiO2、MgO、ZrO2At least one of.
2. the modified tertiary cathode material in surface according to claim 1, which is characterized in that yttria-stabilized zirconia content
Mass percent relative to tertiary cathode material kernel is t, wherein 0.1% < t < 5%；
Another surface modifying species content is s relative to the mass percent of nickelic tertiary cathode material kernel, wherein
0.1% < s < 5%.
3. the modified tertiary cathode material in surface according to claim 1, which is characterized in that in the surface reforming layer, oxygen
Change yttrium stable zirconium oxide chemical formula is Zr(1-a)YaO2-a/2, wherein 0.01 a≤0.3 <, Lacking oxygen amount is 0.01-5000ppm's
Range.
4. the modified tertiary cathode material in surface according to claim 1, which is characterized in that the surface modifying species
Granular size is 0.1-100nm.
5. the preparation method of the modified tertiary cathode material in the described in any item surfaces claim 1-4, which is characterized in that be following
At least one of method:
First method is tertiary cathode material and surface modifying species to be carried out solid phase mixing cladding, by the centre after cladding
Product carries out high-temperature heat treatment process 1, obtains the modified nickelic tertiary cathode material in surface；
Second method is, the presoma of tertiary cathode material, surface modifying species are carried out solid phase mixing cladding, then with list
Water lithium hydroxide is mixed, then carries out high-temperature heat treatment process 2, obtains the modified tertiary cathode material in surface；
The third method is that one of the presoma of tertiary cathode material, surface modifying species are carried out solid phase mixing cladding,
Then after being mixed with monohydrate lithium hydroxide carry out high-temperature heat treatment process 2, obtain intermediate product, by gained intermediate product with
Another progress solid phase mixing cladding in surface modifying species, then high-temperature heat treatment process 1 is carried out, obtain surface is modified three
First positive electrode.
6. preparation method according to claim 5, which is characterized in that the high-temperature heat treatment process 1 are as follows: heat treatment temperature
300-700 DEG C, the time 1-10h of heat treatment.
7. preparation method according to claim 5, which is characterized in that the high-temperature heat treatment process 2 is two sections high warm
Processing, wherein first segment is that 3-10h is heat-treated at a temperature of 400-800 DEG C, and second segment is heat-treated at a temperature of 650-900 DEG C
10-30h。
8. preparation method according to claim 5, which is characterized in that the presoma of the tertiary cathode material is
NixCoyMz(OH)2, wherein M is one of Al, Mn, Ti, Mg, 0 < x <, 1,0 < y <, 1,0 < z < 1.
9. according to the described in any item preparation methods of claim 5-8, which is characterized in that the high-temperature heat treatment process 1, high temperature
Heat treatment procedure 2 is carried out under oxygen atmosphere.
10. the lithium ion battery made of the modified tertiary cathode material in the described in any item surfaces claim 1-4.
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Application publication date: 20181221 Assignee: Youyan New Energy Materials (Jiangxi) Co.,Ltd. Assignor: CHINA AUTOMOTIVE BATTERY RESEARCH INSTITUTE Co.,Ltd. Contract record no.: X2024980000338 Denomination of invention: A surface modified ternary cathode material and its preparation method, as well as a battery made thereof Granted publication date: 20200804 License type: Common License Record date: 20240110 |